CN104520343A - Pla polymer composition - Google Patents

Pla polymer composition Download PDF

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Publication number
CN104520343A
CN104520343A CN201380042310.3A CN201380042310A CN104520343A CN 104520343 A CN104520343 A CN 104520343A CN 201380042310 A CN201380042310 A CN 201380042310A CN 104520343 A CN104520343 A CN 104520343A
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Prior art keywords
composition
polymer
pla
maleic anhydride
agent
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S.基内贝什
J-J.弗拉特
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Arkema France SA
Arkema SA
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Arkema SA
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00—Mixing; Kneading
    • B29B7/30—Mixing; Kneading continuous, with mechanical mixing or kneading devices
    • B29B7/34—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices
    • B29B7/38—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary
    • B29B7/40—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft
    • B29B7/42—Mixing; Kneading continuous, with mechanical mixing or kneading devices with movable mixing or kneading devices rotary with single shaft with screw or helix
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/285—Feeding the extrusion material to the extruder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B29C48/405—Intermeshing co-rotating screws
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/04—Anhydrides, e.g. cyclic anhydrides
    • C08F222/06—Maleic anhydride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/91—Polymers modified by chemical after-treatment
    • C08G63/912—Polymers modified by chemical after-treatment derived from hydroxycarboxylic acids
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/08—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/716—Degradable
    • B32B2307/7163—Biodegradable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/724—Permeability to gases, adsorption
    • B32B2307/7242—Non-permeable
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    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/726—Permeability to liquids, absorption
    • B32B2307/7265—Non-permeable
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Graft Or Block Polymers (AREA)
  • Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Laminated Bodies (AREA)
  • Polyesters Or Polycarbonates (AREA)

Abstract

The present invention relates to a polymer composition, said polymer having a main chain consisting of a polylactic acid, the main chain including a plurality of unsaturated acid anhydride grafts, characterized in that said main chain also includes activating comonomer grafts. The invention also relates to a manufacturing method and to a use linked to said polymer composition.

Description

Based on the polymer composition of PLA
Invention field
The present invention relates to based on poly(lactic acid), more properly there is the polymer composition of the poly(lactic acid) of the specific cografting not making its physical properties demote for providing favourable character of use for it.The invention still further relates to the excellent adhesion character that has comprising described composition to can be used for carry out with coextrusion form the binding agent that uses in multilayered structure.
During the market of " bio-polymer (polymers bio) " (about renewable and/or biodegradable base-material) is in and fully expands, especially in food product pack.This development is owing to needing find the surrogate of fossil material and reduce pollution.The possibility of biorenewable and/or Biodegradable polymeric no longer needs to prove, these polymkeric substance used at most are made up of the polymer composition of poly(lactic acid).
Hereinafter, state " polymer composition " and be interpreted as polymkeric substance, multipolymer and ter-polymers and continuous print composition like this.
With the polymer phase ratio of the fossil sources from nonbiodegradable, these polymkeric substance have the limited impact of environment.The polymkeric substance of biorenewable allows the consumption of restriction fossil material and uses the source from plant crop.Biodegradable polymeric itself fast low be converted into can partially or completely the product that absorbs by the plant that exists in the environment.
But the biological polymer that these former states obtain can not meet all the specification of the raw material of needs in the industry usually, especially in packaging, more particularly when described polymkeric substance must have high-caliber character of use.
In fact, in this field, the structure of use should have excellent machinery, chemical property especially, to barrier properties and/or enough weldabilities of water and air.
Prior art
In order to reach required level (machinery, chemical property etc.), therefore proposing and these biological polymers are combined in multilayered structure.These materials are normally inconsistent, therefore when not using binding agent, can not carry out such combination.In described binding agent, be well known by persons skilled in the art by the use of the polymkeric substance of the graft modification of functional molecule.
Polymer composition based on poly(lactic acid) is such as described in by D. Carlson, L. Nie, R. Narayan, P. Maleation of Polylactide (PLA) by reactive Extrusion (the especially Journal of Applied Polymer Science by name that delivered in 1998 of Dubois, Vol. 72,477-485 (1999)) in.
Therefore, propose, characteristically in above-mentioned article, the functional group be made up of maleic anhydride the free radical approach grafting of molten state thinks that PLA introduces reactive unit.
But, add maleic anhydride graft body by free radical approach at PLA and there is many shortcomings.
First, add maleic anhydride graft body and cause the MFI of PLA (melt flow index) very large raising, make this composition become extremely mobility.But for some application, as the packaging (needing extruded film) of multilayered structure, the MFI of polymer composition should be 1-6 g/10 minute (every 10 minutes grams) at 190 DEG C ideally under 2.16 kilograms.
And, by free radical approach add in PLA maleic anhydride graft body be which provide very bright-coloured orange, it is not suitable for its purposes in many plastic applications, and, more like this when seeking the perfect transparency (namely without the minimal coloring of any painted or transparent film).Therefore, it is desirable for that said composition has lower than 65, preferably lower than 35, more preferably less than the value of 20 in yellowness index test (ASTM E313-96).
Finally, in PLA, add maleic anhydride graft body make PLA thermostability degradation in the molten state.
Should be noted that, polymkeric substance based on PLA has specific chemical structure, it makes it be different from large biological polymer classification, this biological polymer classification especially comprises poly-(hydroxyalkanoate) all or multipolymer or PHA, polyalkylene succinate or PAS, polybutylene succinate adipic acid ester or PBSA, poly-(butylidene) adipic acid ester terephthalate or PBAT, poly-(caprolactone) or PCL, poly-(trimethylene-terephthalate) or PTT, thermoplastic starch or TPS, poly-succsinic acid ethylidene ester or PES, poly-succsinic acid Aden ester or PBS, poly-(butyric ester) or PHB, hydroxybutyrate-co-valerate multipolymer or PHBV, as poly-(3-hydroxybutyrate ester)-poly-(3-hydroxyl valerate), butyric ester capronate multipolymer or PHBHx and butyric ester capronate multipolymer or PHBO.
Just be realised that file JP3134011, which disclose and comprise polycaprolactone (PCL), more properly the embodiment of the composition of polycaprolactone-styrene-maleic anhydride copolymer, but it eliminate PLA.And this file prediction, in order to obtain these compositions, be used in the solvent of about 70 DEG C, and preparation method of the present invention is diverse about 10 hours periods.Finally, the particular technology problem that solution is emphasized in the present invention do not imagined by this file, and this technical problem is resolved by means of the present invention.
Therefore, polymer composition based on the PLA comprising maleic anhydride graft body is very useful thermoplastic material, characteristically consider the functional of them, but until now, also there is not this composition that can overcome shortcoming listed above in the prior art.
Summary of the invention
Surprisingly, the applicant has been found that after test of many times, by means of the grafting body (greffons) adding very particular type, above-mentioned three main drawbacks relevant with the PLA polymer composition comprising maleic anhydride graft body are reduced very significantly, even disappear.
Therefore, the present invention relates to polymer composition, described polymkeric substance has the main chain be made up of poly(lactic acid), and this main chain comprises multiple unsaturated acid anhydride grafting body, is characterised in that described main chain also comprises reactive comonomer grafting body.
The present invention especially has the following advantages:
-meet the rheology of processing industry requirement,
-the more traditional and more acceptable transparency used for variant production, that is, do not have dyeing or very weak dyeing,
The thermostability when molten state of-improvement.
Other feature of the present invention and advantage are described below:
-advantageously, unsaturated acid anhydride grafting body is preferably made up of maleic anhydride;
-advantageously, reactive comonomer grafting body is made up of styrene monomer (monomeres styr é niques);
-preferably, styrene monomer is made up of vinylbenzene;
-according to feature of the present invention, the amount of reactive comonomer is in the composition 0.011 to 2.1 % by weight, to make reactive comonomer described in the composition for 0.01 to 2 molar equivalent of unsaturated acid acid anhydrides;
-preferably, reactive comonomer amount is in the composition 1.2 to 1.9 % by weight, to make reactive comonomer in the composition for 1.1 to 1.8 molar equivalents of unsaturated acid anhydride;
-basis is by possibility provided by the invention, and composition can also comprise the additive existed with 10 to 50000ppm, and wherein said additive comprises antioxidant, UV protective agent, processing aid, as fatty amide, stearic acid and its salt, fluorinated polymer, anti-steam agent, anticlogging agent (agents anti-bloquants), as silicon-dioxide or talcum, static inhibitor, nucleator, staining agent;
-according to feature of the present invention, polymkeric substance also comprises at least one secondary chain be made up of poly(lactic acid).Therefore, common, last polymkeric substance has main chain, can connect thereon, when in preparation/manufacture method, and one or more polylactic acid chain; The latter optionally can comprise the grafting body identical with main chain, i.e. unsaturated acid anhydride grafting body and reactive comonomer grafting body.It should be noted that chain break can occur with grafting phenomenon (producing this chain) simultaneously during preparation is according to polymkeric substance of the present invention; These two kinds of phenomenons simultaneous (fracture and grafting) produce in the final rheology such as introduced in the test carried out below;
-therefore, preferably, secondary chain comprises at least one unsaturated acid anhydride grafting body, preferably maleic anhydride, and/or at least one reactive comonomer grafting body, preferably styrene monomer (monomeres styr é niques), more preferably styrene monomer.
The invention still further relates to the preparation method of the polymer composition according to aforementioned any one of claim, be characterised in that it is included in free radical generating agent, unsaturated acid anhydride, preferably maleic anhydride, and reactive monomer, preferably styrene monomer, when more preferably vinylbenzene exists, uses forcing machine to extrude the step of polylactic acid polymer (PLA); Select temperature during extrusion step to make this polylactic acid polymer to exist with molten state and free radical generating agent decomposes completely during described step.
According to a particular aspect of the invention, polylactic acid polymer (PLA), free radical generating agent, unsaturated acid anhydride and reactive monomer are incorporated in forcing machine simultaneously, or all or part of having carried out of these key elements is pre-mixed to form homogeneous bulk, or is incorporated in forcing machine by all or part of of these key elements simultaneously.
Advantageously, preparation in accordance with the present invention comprises final de-airing step.
Finally, the invention still further relates to multilayered structure, as film or sheet material, it comprises at least three adjacent polymer layers, namely form the middle layer of binding agent, it has the premiere feature being provided in and boning between two perispheres, is characterised in that this middle layer comprises composition as above.
Comprising the multilayered structure of 5 overlapping adjacent layerss under normal circumstances, structure comprises the layer that two are positioned at the formation binding agent of position 2 and 4, and two perispheres (layer 1 and 5) and middle layer (layer 3) are bondd.
And notice, form binding agent and comprise and can comprise other component for providing other machinery/physical/chemical for described layer according to the layer of composition of the present invention.
Two adjacent layerss with comprise as above according to the layer of composition of the present invention in combination, according to technology well known to those skilled in the art, deposit particularly by coextrusion.
As the limiting examples of layer that can form these two adjacent layerss any one (or should both), the composition of layer or the coating disclosed in following file will be mentioned: EP1136536, EP802207, WO97/27259, EP1022310, EP742236, EP1400566, FR2850975, WO01/34389, EP2029672, EP629678, EP1375594, FR2915203, FR2916203.
Detailed Description Of The Invention
Statement polylactic acid polymer is interpreted as such as, the polymkeric substance of the polymkeric substance of lactic acid or multipolymer (PLA) or oxyacetic acid or multipolymer (PGA).
In the context of the present invention, PLA polymkeric substance unsaturated acid anhydride and at least one reactive comonomer carry out cografting.
Notice, as shown in an embodiment, the character of percentage of grafting to polymer composition has material impact.The amount of grafted monomer is passable, such as, easily carried out measuring by means of infrared spectrum technology or the acid base titration (for unsaturated acid anhydride) monitored by potential determination by those skilled in the art and technology (for reactive comonomer) by means of infrared spectra and RMN (nucleus magnetic resonance) spectrum measures.
" reactive comonomer " is interpreted as have undersaturated and be characterized as all monomers of the parameter e of the parameter e value (being 2.25) lower than maleic anhydride here.
(this parameter Q here provides as purely illustrative parameter e and Q, consider it usually and parameter e associatedly exist) be well known by persons skilled in the art, as two parameters of the chart (sch é ma) for Alfrey and Price.In order to obtain detailed information, advantageously with reference to following publication: T. Alfrey Jr. and C. C. Price, J. Polym. Sci. 2,101. (1947).
In fact, by traditional radical copolymerization, the polar effect of monomer close faced by the free radical chain in growth is understood with their two parameter Q and e by the chart of Alfrey and Price.
It is well known that when the gap between the e value of two comonomers increases, the copolymerization trend between two comonomers often increases.
As the example of these reactive monomers, this list does not have exclusiveness feature, is interpreted as styrene monomer." styrene monomer " is construed as in this manual has all monomers of vinylbenzene chemical structure or the combination of monomer.As the example of styrene monomer, can mention: vinylbenzene, alpha-methyl styrene, o-vinyl toluene, m-vinyl toluene, p-methylstyrene, ethyl styrene, isopropenyl toluene, vinyl naphthalene, pseudoallyl naphthalene, vinyl biphenyl base, dimethyl styrene, tert-butyl vinylbenzene, hydroxy styrenes, alkoxystyrene, acetoxy-styrene, bromstyrol, chloro-styrene, vinyl benzoic acid, styracin or styracin alkyl ester.
" reactive comonomer " is also interpreted as 1,1-diphenylethylene, stilbene, phenylacetylene, vinyl pyridine, 2-pseudoallyl naphthalene, divinyl, isoprene, dimethylbutadiene, cyclopentadiene, alkyl vinyl ether, alkyl vinyl thioether, Vinyl phenyl ether, alkyl phenyl vinyl ether, vinyl-acetic ester, methyl methacrylate, naphthyl, furans, indoles, vinyl indoles, NVP, N-vinylcarbazole and vinylchlorid.
Styrene monomer represents preferred reactive comonomer, more preferably vinylbenzene.
With unsaturated acid anhydride grafting body relatively, about grafted monomer, it can be selected from unsaturated carboxylic acid or their functional derivatives.
The example of unsaturated carboxylic acid has those of 2-20 carbon atom, as vinylformic acid, and methacrylic acid, toxilic acid, fumaric acid and methylene-succinic acid.
The functional derivatives of these unsaturated carboxylic acids comprises the metal-salt (as an alkali metal salt) of acid anhydrides, ester derivative, amide derivatives, imide derivative and these unsaturated carboxylic acids.
Have the unsaturated dicarboxylic acid of 4-10 carbon atom and their functional derivatives, especially their acid anhydrides, grafted monomer is preferred especially.
These grafted monomer comprise, such as toxilic acid, fumaric acid, methylene-succinic acid, citraconic acid, allyl succinic acid, hexamethylene-4-alkene-1, 2-dioctyl phthalate, 4-methyl-cyclohexyl-4-alkene-1.2-dioctyl phthalate, dicyclo (2, 2, 1)-heptan-5-alkene-2, 3-dioctyl phthalate, x-methyl bicycle (2, 2, 1)-heptan-5-alkene-2, 3-dioctyl phthalate and their functional derivatives, maleic anhydride, itaconic anhydride, citraconic anhydride, allyl succinic anhydride acid anhydride, hexamethylene-4-alkene-1, 2-dicarboxylic anhydride, 4-methylenecyclohex-4-alkene-1, 2-dicarboxylic anhydride, dicyclo (2, 2, 1) heptan-5-alkene-2, 3-dicarboxylic anhydride, with x-methyl bicycle (2, 2, 1) heptan-5-alkene-2, 2-dicarboxylic anhydride.
Preferred maleic anhydride (writing a Chinese character in simplified form MAH).
And, other component be known in the art can be joined in graftomer of the present invention to improve the character of final material.In these components, normally used additive during processable polymer can be mentioned, such as content is 10ppm-50000ppm's, as antioxidant, UV protective agent, processing aid (agent de mise en oeuvre) is as fatty amide, stearic acid and its salt, the known fluorinated polymer being used as the reagent avoiding extruding defect, anti-fogging agent (agent anti-bu é e), anticlogging agent, as silicon-dioxide or talcum.The additive of other type can also be added into the special properties providing hope.Such as static inhibitor will be mentioned, nucleator, staining agent.
according to the preparation of composition of the present invention:
About the acquisition of the composition of the PLA based on maleic anhydride graft, various currently known methods (reactive extrursion method, solution form, by irradiating or solid state) can be used to make functional monomer if maleic anhydride graft is on PLA polymkeric substance.As an example, the grafting of maleic anhydride on PLA polymkeric substance can be implemented when free radical generating agent exists in the molten state in an extruder.Operable suitable free radical generating agent comprises the tertiary butyl-hydroperoxide, cumene-hydroperoxide, two-iso-propyl group-benzene-hydroperoxide, two-tert-butyl-peroxy compound, two-t-amyl group-superoxide, the tertiary butyl-cumyl-superoxide, dicumyl-superoxide, 1, 3-pair-(t-butyl peroxy-sec.-propyl) benzene, 2, 5-dimethyl-2, 5-bis-(t-butyl peroxy) hexane, tert-butyl-peroxy benzoic ether, t-butyl-peroxide-2-ethylhexanoate, the OO-tertiary butyl-O-(2-ethyl hexyl)-mono-peroxy carbonates, OO-t-amyl group-O-(2-ethyl hexyl)-mono-peroxy carbonates, ethanoyl-superoxide, dibenzoyl-superoxide, isobutyryl-superoxide, two-3, 5, 5-trimethylammonium-caproyl-superoxide and methyl-ethyl-ketone-superoxide.
Styrene monomer and the cografting of maleic anhydride on PLA is related more particularly to according to the preparation method of composition of the present invention.This preparation method forms by extruding PLA polymkeric substance in homodromal twin screw extruder when free radical generating agent, maleic anhydride and styrene monomer exist.Selective temperature is to make this reaction carry out when the molten state of polymkeric substance and to make free radical generating agent decompose completely distributing in the time extruded.Notice and degassedly to carry out with the degradation production extracting free radical generating agent from PLA polymkeric substance and unreacted monomer at forcing machine end.
embodiment according to composition of the present invention:
Composition based on the PLA of maleic anhydride and styrene monomer grafting is prepared in the homodromal twin screw extruder of Haake PTW 16/25.The PLA the used Ingeo 2003D that is NatureWork, the vinylbenzene of styrene monomer for being provided by Aldrich company of use, it is the Luperox 101 of Arkema company that maleic anhydride is provided with free radical generating agent by CristalMan company.The charging of forcing machine is quantitatively counted by weight and is provided.In order to ensure the uniform charging of composition, in charging, this has carried out mixing in bag before quantitatively counting the different components of preparaton.For this reason, PLA carries out use and liquid ingredient (vinylbenzene and Luperox 101) has been submerged on PLA powder in powder form.Extrusion condition is: flow=1kg/h, temperature=180 DEG C and screw speed=100rpm.Forcing machine is equipped with degassed trap (puits de d é gazage), and it allows to make resistates devolatilization (in degassed trap P=-0.95 bar) at forcing machine end by means of impeller pump.Carry out cooling when the maleic anhydride left from forcing machine is contacted with air with styrene-grafted PLA polymkeric substance on transport tape and being then granulated by means of ring pelletizer (granulateur à jonc).The amount of the maleic anhydride introduced is 1 quality %, relative to the total mass of different components.The amount of the Luperox 101 introduced is 0.4 quality %.The cinnamic amount introduced is cinnamic amount that 0-1.8 quality % makes the to introduce 0-1.7 molar equivalent that is introduced maleic anhydride.
test to described composition carries out:
The composition of test is following:
-n ° of 1 composition: based on the composition (without styrene monomer) of the PLA of maleic anhydride graft
-n ° of 2 compositions: based on the composition of the PLA of maleic anhydride and 0.5 equivalent styrene class monomer cografting
-n ° of 3 compositions: based on the composition of the PLA of maleic anhydride and 1 equivalent styrene class monomer cografting
-n ° of 4 compositions: based on the composition of the PLA of maleic anhydride and 1.2 equivalent styrene class monomer cograftings
-n ° of 5 compositions: based on the composition of the PLA of maleic anhydride and 1.5 equivalent styrene class monomer cograftings
-n ° of 6 compositions: based on the composition of the PLA of maleic anhydride and 1.7 equivalent styrene class monomer cograftings
-composition PLA 2003D: from the Ingeo 2003D poly (lactic acid) composition (without maleic anhydride graft body and styrenic grafting body) of Nature Work company.
Statement maleic anhydride and X equivalent styrene class monomer cografting be interpreted as in considered PLA, for (1) maleic anhydride molecule, during graft reaction, there is X styrene monomer molecule.
Statement grafting body, is interpreted as maleic anhydride or styrene monomer, the maleic anhydride of directly or indirectly grafting on PLA chain or any sequence of styrene monomer.Therefore, grafting body can be made up of the separate unit of grafting on described PLA chain, and in this case, described grafting body is counted into as maleic anhydride units or styrene-type monomer units.But, statement grafting body can also be made up of the branch (ramification) of grafting on PLA chain, described branch comprises one or more maleic anhydride units and/or styrene-type monomer units, in this case, the number of the maleic anhydride units existed in considered branch should be counted as maleic anhydride graft body, and the number of the styrene-type monomer units existed in considered branch should be counted as styrene monomer grafting body.
mFI tests:
The first enforcement described composition is tested as to measure MFI (Melt Flow Inx) according to standard ISO 1133 at 190 DEG C (degree Celsius) under 2.16kg (kilogram):
The MFI measured
N ° of 1 composition 18
N ° of 2 compositions 13.3
N ° of 3 compositions 9.2
N ° of 4 compositions 5.8
N ° of 5 compositions 2
N ° of 6 compositions 1.4
The PLA 2003D extruded 3
dyeing test:
The second test carried out described composition is the yellowness index measured according to standard A STM E313-96:
Yellowness index
N ° of 1 sample 92
N ° of 2 samples 65
N ° of 3 samples 35
N ° of 4 samples 20
N ° of 5 samples 15
N ° of 6 samples 12
The PLA 2003D extruded 10
heat stability testing
To described composition carry out the 3rd and last test be measure at 180 DEG C, (PHYSICA MCR301 rheometer, the parallel planes of direct 25mm, at 1rad.s under nitrogen flowing -1time 10 minutes).The measurement of this thermostability is with at 180 DEG C with at 1rad.s -1viscosity represent according to the change % of time.
To notice, maleic anhydride and styrene monomer cografting is used to implement to the test of composition according to the present invention, but contriver can sum up their result, possibly, use all unsaturated acid anhydrides listed above and reactive comonomer respectively, there is or worse advantage more less a little than the result using this specific cografting to obtain.

Claims (13)

1. polymer composition, described polymkeric substance has the main chain be made up of poly(lactic acid), and this main chain comprises multiple unsaturated acid anhydride grafting body, is characterised in that described main chain also comprises reactive comonomer grafting body.
2. composition according to claim 1, is characterised in that described unsaturated acid anhydride grafting body is made up of maleic anhydride.
3., according to the composition of claim 1 or 2, be characterised in that described reactive comonomer grafting body is made up of styrene monomer.
4. composition according to claim 3, is characterised in that described styrene monomer is made up of vinylbenzene.
5. according to the composition of aforementioned any one of claim, be characterised in that the amount of reactive comonomer is in the composition 0.011 to 2.1 % by weight, to make reactive comonomer in the composition for 0.01 to 2 molar equivalent of unsaturated acid acid anhydrides.
6. composition according to claim 5, is characterised in that the amount of reactive comonomer is in the composition 1.2 to 1.9 % by weight, to make reactive comonomer in the composition for 1.1 to 1.8 molar equivalents of unsaturated acid anhydride.
7. according to the composition of aforementioned any one of claim, be characterised in that composition also comprises the additive existed with 10 to 50000ppm, and be that described additive comprises antioxidant, UV protective agent, processing aid, as fatty amide, stearic acid and its salt, fluorinated polymer, anti-steam agent, anticlogging agent, as silicon-dioxide or talcum, static inhibitor, nucleator, staining agent.
8., according to the composition of aforementioned any one of claim, be characterised in that the secondary chain that polymkeric substance also comprises at least one and is made up of poly(lactic acid).
9. composition according to claim 8, is characterised in that described chain comprises at least one unsaturated acid anhydride grafting body, preferably maleic anhydride, and/or at least one reactive comonomer grafting body, preferably styrene monomer, more preferably styrene monomer.
10. for the preparation of the method for the polymer composition according to aforementioned any one of claim, be characterised in that it is included in free radical generating agent, unsaturated acid anhydride, preferably maleic anhydride, and reactive monomer, preferably styrene monomer, when more preferably styrene monomer exists, uses forcing machine to extrude the step of polylactic acid polymer (PLA); Select temperature during this extrusion step to make this polylactic acid polymer to exist with molten state and free radical generating agent decomposes completely during described step.
11. methods according to claim 10, be characterised in that and polylactic acid polymer (PLA), free radical generating agent, unsaturated acid anhydride and reactive monomer are incorporated in forcing machine simultaneously, or all or part of having carried out of these key elements is pre-mixed to form homogeneous bulk, or is incorporated in forcing machine by all or part of of these key elements simultaneously.
12., according to the method for claim 10 or 11, are characterised in that it comprises final de-airing step.
13. multilayered structures, as film or sheet material, it comprises at least three adjacent polymer layers, namely forms the middle layer of binding agent, it has the premiere feature of the bonding be provided between two perispheres, is characterised in that this middle layer comprises the composition as described in any one of claim 1-9.
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